Synthesis of hydrofluoroalkanols and hydrofluoroalkenes

ABSTRACT

Described herein is a process for the manufacture of hydrofluoroalkanols of the structure R f CFClCHROH. Also described herein are methods of manufacturing hydrofluoroalkenes of the structure R f CF═CHR from halofluorocarbons of the structure R f CFX 2 . In particular, 2,3,3,3,-tetrafluoro-1-propene may be manufactured with this process. Also described are compounds of the formula R f CFClCHROC(═O)R′.

CROSS REFERENCE(S) TO RELATED APPLICATION(S)

This application is a divisional of pending U.S. patent application Ser.No. 12/274,728, filed Nov. 20, 2008, which claims the priority benefitof Ukrainian Patent Application No. A200712916, filed Nov. 21, 2007 andU.S. Provisional Patent Application 61/104,334, filed Oct. 10, 2008.

BACKGROUND

1. Field of the Disclosure

This disclosure relates in general to a process for the production ofhydrofluoroalkanols, and a process for the production ofhydrofluoroalkenes, and in particular a process for the production of2,3,3,3-tetrafluoro-1-propene, from hydrofluoroalkanols andhydrofluoroalkanol esters.

2. Description of the Related Art

The refrigeration industry has been working for the past few decades tofind replacement refrigerants for the ozone depletingchlorofluorocarbons (CFC's) and hydrochlorofluorocarbons (HCFC's) beingphased out as a result of the Montreal Protocol. The solution for mostrefrigerant producers has been the commercialization ofhydrofluorocarbon (HFC) refrigerants. HFC's, however, are now beingregulated due to concerns related to global warming.

There is always a need for new and better processes for the preparationof halocarbons that may be useful as refrigerants or in otherapplications such as foam expansion agents, aerosol propellants, firesuppression or extinguishing agents, solvents, and sterilants to name afew.

SUMMARY OF THE INVENTION

The present invention provides for the manufacture ofhydrofluoroalkanols and hydrofluoroalkenes. Described herein is aprocess for the manufacture of hydrofluoroalkanols of the structureR_(f)CFXCHROH, comprising reacting a halofluorocarbon of the structureR_(f)CFX₂, wherein each X is independently selected from Cl, Br, and I,with an aldehyde and a reactive metal in a reaction solvent to generatea reaction product comprising a metal hydrofluoroalkoxide, neutralizingsaid the metal hydrofluoroalkoxide to produce a hydrofluoroalkanol, and,optionally, recovering the hydrofluoroalkanol.

Also described herein are methods of manufacturing hydrofluoroalkenesfrom halofluorocarbons of the structure R_(f)CFX₂, wherein each X isindependently selected from Cl, Br, and I, comprising reactinghalofluorocarbons of the structure R_(f)CFX₂, wherein each X isindependently selected from Cl, Br, and I with an aldehyde and areactive metal in a reaction solvent to generate a reaction productcomprising a metal hydrofluoroalkoxide, and reductivelydehydroxyhalogenating the metal hydrofluoroalkoxide to produce ahydrofluoroalkene, and, optionally, recovering the hydrofluoroalkene. Inone embodiment, the reductive dehydroxyhalogenation comprises reactingthe metal hydrofluoroalkoxide with a carboxylic acid anhydride and areactive metal to form the hydrofluoroalkene. In another embodiment, thereductive dehydroxyhalogenation comprises neutralizing the metalhydrofluoroalkoxide to produce a hydrofluoroalkanol, mixing adehydrating agent with said hydrofluoroalkanol thereby forming a gaseousmixture, and contacting a catalyst with said gaseous mixture, therebyforming the hydrofluoroalkene.

Also described herein are methods of manufacturing2,3,3,3-tetrafluoro-1-propene. The methods comprise the steps ofmanufacturing hydrofluoroalkenes as described above, wherein R_(f) isCF₃.

Also disclosed herein are novel hydrofluoroalkanol esters of the formulaR_(f)CFXCH₂OC(═O)R, where R_(f) is a perfluoroalkyl group having fromone to four carbon atoms, R is CH₃, CH₃CH₂, CH₃CH₂CH₂, (CH₃)₂CH or H, Xis selected from Cl, Br, and I, and R′ is selected from the groupconsisting of —CH₃, —C₂H₅, —CH₂CH₂CH₃, CH₂CH₂CO₂H, CH₂CH₂CH₂CO₂H,CH₂CH₂CH₂CH₂CO₂H and H, and novel hydrofluorocarbons of the formulacyclo-(—CF(R_(f))CHRCF(R_(f))CHR—).

Also disclosed is a method for the manufacture of hydrofluoroalkenes ofthe structure R_(f)CF═CHR, comprising reacting a hydrofluoroalkanol ofstructure R_(f)CFXCHROH or a hydrofluoroalkoxide of structureR_(f)CFXCHROMX, wherein M is a reactive metal in the +2 oxidation stateand wherein X is selected from Cl, Br, and I, with a carboxylic acidanhydride and a reactive metal in a reaction solvent to form ahydrofluoroalkene, and isolating the hydrofluoroalkene.

Also disclosed herein is a compound having the formulaR_(f)CFXCHRO—Zn—X, where R_(f) is a perfluoroalkyl group having from oneto four carbon atoms, X is selected from Cl, Br, and I, and R is CH₃,CH₃CH₂, CH₃CH₂CH₂, (CH₃)₂CH or H.

Many aspects and embodiments have been described above and are merelyexemplary and not limiting. After reading this specification, skilledartisans appreciate that other aspects and embodiments are possiblewithout departing from the scope of the invention.

Other features and benefits of any one or more of the embodiments willbe apparent from the following detailed description and from the claims.

DETAILED DESCRIPTION

Before addressing details of embodiments described below, some terms aredefined or clarified.

As used herein, formaldehyde refers to the compound having the structureH₂C═O, which is also known to occur in the form of a cyclic trimer1,3,5-trioxane, and also as paraformaldehyde or polyoxymethylene.

As used herein, reactive metal refers to reactive metals such asmagnesium turnings, activated zinc powder, aluminum, and a powder of anyof the following metals: magnesium, calcium, titanium, iron, cobalt,nickel, copper, zinc and indium, and also zinc(II) salts. Magnesiumturnings are pieces of magnesium which are cut to produce small pieceswith higher surface areas and generally low amounts of surface oxides(which reduce reactivity). The reactive metal powders of magnesium,calcium, titanium, iron, cobalt, nickel, copper, zinc and indium areRieke metals, which are prepared by a specific procedure which produceshigh surface area metal powders which are very reactive in reactionssuch as those of the present invention. Without wishing to be bound byany particular theory, Rieke metals are thought to be highly reactivebecause they have high surface areas and lack passivating surfaceoxides.

As used herein, a dehydrating agent is a gas or gaseous mixturecontaining at least one gas selected from the group consisting of:methane, ethane, propane, butane, natural gas, alcohols, aldehydes, andcarbon monoxide. As used herein, natural gas refers to a gaseous mixturehaving methane as the major component, but also comprising quantities ofethane, butane, propane, carbon dioxide, nitrogen.

As used herein dehydroxyhalogenating refers to removing a hydroxyl groupand a halogen atom, chosen from Cl, Br and I, from adjacent carbon atomsof a hydrofluoroalkanol to form a hydrofluoroalkene.

In one embodiment, hydrofluoroalkanols of the formula R_(f)CFXCHROH,such as 1,1,1,2-tetrafluoro-2-chloropropanol, an intermediate that maybe converted into 2,3,3,3-tetrafluoro-1-propene (HFC-1234yf), areprepared. In one embodiment, R is selected from the group consisting ofCH₃, CH₃CH₂, CH₃CH₂CH₂, (CH₃)₂CH or H. In one embodiment, R_(f) is aperfluoroalkyl group having from one to four carbon atoms. In anotherembodiment, R_(f) is selected from the group consisting ofperfluoromethyl, perfluoroethyl, perfluoro-n-propyl, perfluoro-i-propyl,perfluoro-n-butyl and perfluoro-i-butyl, respectively, i.e., CF₃—,CF₃CF₂—, CF₃CF₂CF₂—, (CF₃)₂CF—, CF₃CF₂CF₂CF₂— and CF₃CF(CF₃)CF₂—,respectively. In one embodiment, R_(f) is CF₃ and R is H. In oneembodiment X is selected from Cl, Br, and I. In another embodiment, X isCl.

In one embodiment, halofluorocarbons of the formula R_(f)CFX₂, whereineach X is independently selected from Cl, Br, and I, are reacted with analdehyde, and a reactive metal in a reaction solvent to generate a metalhydrofluoroalkoxide. In one embodiment the metal hydrofluoroalkoxide isneutralized to provide a hydrofluoroalkanol, which can be isolated. Insome embodiments, the neutralization comprises dilution with an organicsolvent, and reaction with a dilute aqueous solution of an acid,including without limitation dilute aqueous hydrochloric acid or diluteaqueous sulfuric acid. Upon separation of the organic solvent phase fromthe aqueous phase, in some embodiments, the organic solvent phase iswashed further with an aqueous salt solution. The organic solvent phaseis then dried and the solvent removed by evaporation or distillation toprovide the hydrofluoroalkanol product. In other embodiments, the metalhydrofluoroalkoxide may be used in further reactions as described laterto produce a hydrofluoroalkene without neutralization. In oneembodiment, the halofluorocarbon is 1,1,dichlorotetrafluoroethane andthe hydrofluoroalkanol is 2-chloro-2,3,3,3-tetrafluoro-1-propanol.

Halofluorocarbons of the formula R_(f)CFX₂, wherein each X isindependently selected from Cl, Br, and I may be prepared byhalogenation of the corresponding hydrofluorocarbons R_(f)CFH₂. Forexample, in one embodiment where R_(f) is CF₃ and X is Cl,1,1,1,2-tetrafluoroethane (HFC-134a) is chlorinated to prepare1,1,1,2-tetrafluoro-2,2-dichloroethane (CFC-114a).

In some embodiments, in addition to the reactive metal, a zinc salt isadded to the mixture comprising the reaction of the halofluorocarbon.Suitable zinc salts include zinc acetate, zinc bromide, zinc chloride,zinc citrate, zinc sulfate and mixtures thereof. In one embodiment, thezinc salt is zinc acetate. In one embodiment, the amount of zinc saltadded is from 0.1 to 1.0 mole per mole of halofluorocarbon. In anotherembodiment, the amount of zinc salt added is from 0.25 to 0.7 mole permole of halofluorocarbon. In another embodiment, the amount of zinc saltadded is from 0.5 to 0.6 mole per mole of halofluorocarbon.

In one embodiment, the aldehyde is selected from the group consisting offormaldehyde, acetaldehyde, propionaldehyde, butyraldehyde andisobutyraldehyde. In one embodiment, the mole ratio of reactive metal tohalofluorocarbon is about 1:1. In another embodiment, the mole ratio ofreactive metal to halofluorocarbon is about 2:1. In yet anotherembodiment, the mole ratio of reactive metal to halofluorocarbon isabout 2.5:1. In one embodiment, the mole ratio of aldehyde tohalofluorocarbon is about 1:1. In another embodiment, the mole ratio ofaldehyde to halofluorocarbon is about 2:1. In yet another embodiment,the mole ratio of aldehyde to halofluorocarbon is about 3:1.

In some embodiments where paraformaldehyde is used as the aldehyde, aquaternary ammonium salt is added to the reaction. In one embodiment,the quaternary ammonium salt is a bis-alkyldimethyl ammonium acetate.Without wishing to be bound by any particular theory, such quaternaryammonium salts are believed to promote the decomposition ofparaformaldehyde to formaldehyde. In some embodiments the amount ofquaternary ammonium salt added is from about 1% to about 20% by weightof the amount of paraformaldehyde. In other embodiments, the amount ofquaternary ammonium salt added is from about 5% to about 10% by weightof the amount of paraformaldehyde.

The reaction of the halofluorocarbon with an aldehyde and reactive metalis conducted in a reaction solvent. In one embodiment, the reactionsolvent is selected from the group consisting of alkyl, dialkyl, andtrialkyl linear or cylic amines, N-methylpyrrolidine,N-methylpiperidine, sulfoxides, ethers, pyridine or alkyl-substitutedpyridines, pyrazine or pyrimidine, alkyl and aromatic nitriles,hexamethylphosphoramide, alcohols, esters, and mixtures thereof. In oneembodiment, an alcohol solvent is methanol. In one embodiment, an estersolvent is methyl formate. In one embodiment, a sulfoxide solvent isdimethylsulfoxide. In one embodiment, an alkyl nitrile solvent isacetonitrile. In one embodiment, an aromatic nitrile solvent isbenzonitrile. In another embodiment, the reaction solvent is selectedfrom the group consisting of trialkylamines, N-methylpyrrolidine,N-methylpiperidine, pyridine, alkyl-substituted pyridines,dimethylformamide, pyrazine or pyrimidine, and mixtures thereof. Inanother embodiment, the reaction solvent is selected from the groupconsisting of dimethylformamide, tetrahydrofuran, pyridine,dimethylacetamide, 1,4-dioxane, N-methylpyrrolidone, diethyl ether, andmixtures thereof. In yet another embodiment, the reaction solvent ispyridine or alkyl-substituted pyridines, or mixtures thereof. In yetanother embodiment, the reaction solvent is a mixture of pyridine oralkyl-substituted pyridines, and dimethylformamide.

In one embodiment, the amount of water present in the reaction of thehalofluorocarbon with an aldehyde and reactive metal is less than 1000ppm. In another embodiment, the amount of water present in the reactionof the halofluorocarbon with an aldehyde and reactive metal is about 500ppm. In yet another embodiment, the amount of water present in thereaction of the halofluorocarbon with an aldehyde and reactive metal isfrom about 100 to about 300 ppm.

In one embodiment, the reaction of the halofluorocarbon with an aldehydeand reactive metal is performed at a temperature of from about 30° C. toabout 100° C. In another embodiment, the reaction of thehalofluorocarbon with an aldehyde and reactive metal is performed at atemperature of from about 50° C. to about 80° C. In one embodiment, thereaction is conducted for from about 3 to about 10 hours. In anotherembodiment, the reaction of the halofluorocarbon with an aldehyde andreactive metal is conducted for from about 4 to about 8 hours. In yetanother embodiment, the reaction of the halofluorocarbon with analdehyde and reactive metal is conducted for from about 4 to about 6hours.

In one embodiment, the aldehyde is pre-treated with the reaction solventfor a period of time before the reaction. In one embodimentparaformaldehyde is pre-treated in pyridine for four hours at 60° C.prior to reaction with halofluorocarbon and reactive metal. In oneembodiment, the pre-treatment occurs for two hours. In anotherembodiment, the pre-treatment occurs for six hours. In still otherembodiments, there is no pre-treatment, and the reaction is commencedupon charging all of the reactants and reaction solvent to the reactionvessel sequentially.

In one embodiment, the reaction of the halofluorocarbon with an aldehydeand reactive metal is performed in a closed vessel or other reactor. Inone embodiment the reaction of the halofluorocarbon with an aldehyde andreactive metal is performed under autogenous pressure. In anotherembodiment, the reaction of the halofluorocarbon with an aldehyde andreactive metal is performed in an open vessel or reactor, equipped witha suitable condenser to prevent escape of unreacted halofluorocarbon.

According to another aspect of the present invention, there is provideda process for the manufacture of hydrofluoroalkenes of the structureR_(f)CF═CHR. This process comprises reacting a halofluorocarbon of thestructure R_(f)CFX₂ with an aldehyde and a reactive metal to generate ametal hydrofluoroalkoxide, reductively dehydroxyhalogenating saidreaction product in a second step to produce a hydrofluoroalkene, andthen isolating the hydrofluoroalkene.

In one embodiment, R_(f) is a perfluoroalkyl group having from one tofour carbon atoms. In a particular embodiment, R_(f) is CF₃ and R is H.

In one embodiment, the process for producing a hydrofluoroalkenecomprises neutralizing the reaction product to produce ahydrofluoroalkanol; mixing a dehydrating agent with thehydrofluoroalkanol, thereby forming a gaseous mixture; and contacting acatalyst with the gaseous mixture, thereby forming thehydrofluoroalkene.

In one embodiment, the reaction product of a chlorofluoroalkane, analdehyde and a reactive metal is neutralized by diluting the reactionproduct mixture with a mixture of a solvent, ice, and an aqueoussolution of an acid. In one embodiment, the solvent can be any commonlyused organic solvent, such as diethyl ether. In one embodiment, theaqueous solution of an acid is an aqueous solution of a common mineralacid, such as hydrochloric acid. After stirring the resulting mixturefor a period of time, the layer comprising the organic solvent isseparated. In one embodiment, the organic solvent layer can besubsequently washed with a dilute aqueous solution of an acid, followedby a brine solution. The organic layer is then dried. In someembodiments, the drying is accomplished by stirring the organic layerover and anhydrous salt, such as anhydrous magnesium sulfate oranhydrous sodium sulfate. In some embodiments, the organic solvent canthen be evaporated to afford the hydrofluoroalkanol.

In this embodiment, the hydrofluoroalkanol is at least one selected fromthe group consisting of: fluoroalkanols having the general formulaR_(f)′CH₂OH wherein R_(f)′ is selected from the group consisting of:CF₃CFCl—, CF₃CF₂CFCl—, CF₃CF₂CF₂CFCl— and CF₃CF₂CF₂CF₂CFCl—. In oneembodiment, the hydrofluoroalkanol is2,3,3,3-tetrafluoro-2-chloro-1-propanol.

In one embodiment, the catalyst is at least one transition metal. Themetal is selected from the group consisting of: nickel (Ni), palladium(Pd), and platinum (Pt). In one embodiment, the catalyst is a supportedcatalyst which comprises a transition metal and a support material. Thesupport material is at least one selected from the group consisting ofactivated carbon and λ-alumina.

The dehydrating agent is at least one gas selected from the groupconsisting of: methane, ethane, propane, butane, natural gas, alcohols,aldehydes, and carbon monoxide.

The mixing step takes place at a temperature in the range between about65-80° C.

The process further comprises preheating the gaseous mixture prior tothe contacting step. The preheating takes place at a temperature in therange between about 250 to about 450° C.

The contacting step preferably takes place at a temperature in the rangebetween about 400 to about 700° C. The contacting step also preferablytakes place for between about 20 to about 25 seconds.

The process further comprises the step of neutralizing any residual HFcontained in the hydrofluoroalkene product, wherein the HF isneutralized by passing the hydrofluoroalkene product through a KOHsolution.

The hydrofluoroalkene product comprises at least one hydrofluoroalkeneselected from the group consisting of: 2,3,3,3-tetrafluoro-1-propene orany hydrofluoroalkene selected from the group consisting of compoundsrepresented by the formula: R_(f)CF═CH₂ wherein R_(f) is selected fromthe group consisting of: CF₃, CF₃CF₂, CF₃CF₂CF₂, (CF₃)₂CF—,CF₃CF₂CF₂CF₂— and CF₃CF(CF₃)CF₂—.

The gaseous mixture may further comprise at least one diluent inert gasselected from the group consisting of: nitrogen, helium, and argon.

The conversion of the hydrofluoroalkanol to hydrofluoroalkene is in therange between about 50 to about 100%. The selectivity ofhydrofluoroalkanol to hydrofluoroalkene is in the range between about 29to about 100%.

The pressure during the contacting step is in the range between about 1to about 100 psig.

Further in accordance with the present invention, there is provided aprocess for the manufacture of hydrofluoroalkenes of the structureR_(f)CF═CHR, comprising reacting a hydrofluoroalkanol of structureR_(f)CFXCHROH or a hydrofluoroalkoxide of structure R_(f)CFXCHROMX,wherein M is a reactive metal in the +2 oxidation state, with acarboxylic acid anhydride and a reactive metal in a reaction solvent toform a hydrofluoroalkene, and isolating the hydrofluoroalkene.

In another embodiment, the reductive dehydroxyhalogenation comprisesreacting the metal hydrofluoroalkoxide with a carboxylic acid anhydrideand a reactive metal. In this embodiment, hydrofluoroalkenes of thestructure R_(f)CF═CHR are manufactured by reacting a hydrofluoroalkanolof structure R_(f)CFXCHROH or a hydrofluoroalkoxide of structureR_(f)CFXCHROMX, wherein M is a reactive metal in the +2 oxidation state,with a carboxylic acid anhydride and a reactive metal in a reactionsolvent to form a hydrofluoroalkene, and optionally, isolating thehydrofluoroalkene. In this embodiment, the hydrofluoroalkanol ofstructure R_(f)CFXCHROH or a hydrofluoroalkoxide of structureR_(f)CFXCHROMX, wherein M is a reactive metal in the +2 oxidation state,react first with the carboxylic acid anhydride to form an ester asdescribed below. This ester then reacts with the reactive metal to forma hydrofluoroalkene. In this process R_(f) is selected from the groupconsisting of perfluoromethyl, perfluoroethyl, perfluoro-n-propyl,perfluoro-i-propyl, perfluoro-n-butyl and perfluoro-i-butyl, X isselected from Cl, Br, and I, and R is selected from the group consistingof H, CH₃, C₂H₅, n-C₃H₇, and i-C₃H₇, and in particular R_(f) is CF₃, Xis Cl and R is H. In this process the carboxylic acid anhydride isselected from the group consisting of acetic anhydride, propionicanhydride, butyric anhydride, succinic anhydride, glutaric anhydride,adipic anhydride, and formic anhydride. The reactive metal powder is asdescribed above. In some embodiments of this process, the reductivedehydroxyhalogenation can be done without neutralizing the productmixture from the reaction of a halofluorocarbon with a reactive metaland an aldehyde. In other embodiments, the reductivedehydroxyhalogenation is done after first isolating thehydrofluoroalkanol, and then reacting it with a carboxylic acidanhydride and a reactive metal. In some embodiments, the reductivedehydroxyhalogenation is done without isolating the ester. In otherembodiments, the reductive dehydroxyhalogenation is done with the esterbeing isolated from the solvent and metal salts, and then reacted withthe reactive metal.

In some embodiments, the product of the reductive dehydroxyhalogenationfurther comprises a substituted cyclobutane of the formulacyclo-(—CF(R_(f))CHRCF(R_(f))CHR—), wherein R_(f) is a perfluoroalkylgroup having from one to four carbon atoms and R is CH₃, CH₃CH₂,CH₃CH₂CH₂, (CH₃)₂CH or H. In one particular embodiment, R_(f) is CF₃ andR is H.

In one embodiment, the carboxylic acid anhydride is selected from thegroup consisting of acetic anhydride, propionic anhydride, butyricanhydride, succinic anhydride, glutaric anhydride, adipic anhydride, andformic anhydride. In another embodiment, the carboxylic acid anhydrideis acetic anhydride. In one embodiment, the mole ratio of carboxylicacid anhydride to hydrofluoroalkanol is from about 1:1 to about 2:1. Inanother embodiment, the mole ratio of carboxylic acid anhydride tohydrofluoroalkanol is from about 1.4:1 to about 1.8:1. In oneembodiment, the mole ratio of reactive metal to hydrofluoroalkanol isabout 1:1. In another embodiment, the mole ratio of reactive metal tohydrofluoroalkanol is about 2:1. In yet another embodiment, the moleratio of reactive metal to hydrofluoroalkanol is about 2.5:1. Thereaction between the metal hydrofluoroalkoxide and the carboxylic acidanhydride produces an ester of the formula R_(f)CFXCHROC(═O)R′ whereR_(f) is as described above, R is as described above, X is as describedabove, and R′ is the residue from the carboxylic acid anhydridesdescribed above, and is selected from the group consisting of —CH₃,—C₂H₅, —CH₂CH₂CH₃, CH₂CH₂CO₂H, CH₂CH₂CH₂CO₂H, CH₂CH₂CH₂CH₂CO₂H, and H.In one embodiment, R_(f) is CF₃, R is H, X is Cl, and R′ is CH₃.

In one embodiment, the reductive dehydroxyhalogenation is conducted in areaction solvent which is the same solvent in which the reaction of ahalofluorocarbon with reactive metal and an aldehyde is conducted in. Inanother embodiment, the reductive dehydroxyhalogenation is conducted ina reaction solvent which is a different solvent than the reaction of ahalofluorocarbon with reactive metal and an aldehyde is conducted in. Inyet another embodiment, the reductive dehydroxyhalogenation is conductedin a mixture of pyridine or an alkyl-substituted pyridine, anddimethylformamide.

In one embodiment, the product of the esterification of thehydrofluoroalkanol is a compound having the formula: R_(f)CFXCHROC(═O)R′where R_(f) is a perfluoroalkyl group having from one to four carbonatoms, R is CH₃, CH₃CH₂, CH₃CH₂CH₂, (CH₃)₂CH or H, X is selected fromCl, Br, and I, and R′ is selected from the group consisting of —CH₃,—C₂H₅, —CH₂CH₂CH₃, CH₂CH₂CO₂H, CH₂CH₂CH₂CO₂H, CH₂CH₂CH₂CH₂CO₂H and H.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

Also, use of “a” or “an” are employed to describe elements andcomponents described herein. This is done merely for convenience and togive a general sense of the scope of the invention. This descriptionshould be read to include one or at least one and the singular alsoincludes the plural unless it is obvious that it is meant otherwise.

Group numbers corresponding to columns within the Periodic Table of theelements use the “New Notation” convention as seen in the CRC Handbookof Chemistry and Physics, 81^(st) Edition (2000-2001).

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of embodiments of the present invention, suitablemethods and materials are described below. All publications, patentapplications, patents, and other references mentioned herein areincorporated by reference in their entirety, unless a particular passageis cited. In case of conflict, the present specification, includingdefinitions, will control. In addition, the materials, methods, andexamples are illustrative only and not intended to be limiting.

EXAMPLES

The concepts described herein will be further described in the followingexamples, which do not limit the scope of the invention described in theclaims.

Example 1

Example 1 demonstrates the preparation of2-chloro-3,3,3-trifluoropropanol from1,1,1,2-tetrafluoro-2,2-dichloroethane.

A 400 ml Hastelloy C shaker tube was charged with 32.8 g (0.5 mol) ofactivated Zinc powder, 12 g (0.5 mol) of paraformaldehyde and 180 mlanhydrous DMF under N₂. The tube was cooled down to −15° C. and 64.4 g(0.2 mol) of 1,1-dichlorotetrafluoroethane were added. Then the reactionmixture was stirred at 50° C. for 6 hours. The results of gaschromatography analysis of the reaction are summarized in Table 1. Afterthe reaction mixture cooled down to room temperature, it was poured intoa 200 ml mixture of ice, 10% aqueous HCl and 200 ml diethyl ether withstirring. After another 30 min stirring, the organic layer was separatedand washed with 100 mL of 2% aqueous HCl and then 100 mL brine. After itwas dried with MgSO₄, diethyl either was removed by vacuum to afford13.36 of product (yield 8%).

TABLE 1 Component GC area percent (%)2-chloro-2,3,3,3-tetrafluoropropanol 7.0762-chloro-1,1,1,2-tetrafluoroethane 8.18 Methanol .335 DMF 83.9

Example 2

Example 2 demonstrates the conversion of2-chloro-2,3,3,3-tetrafluoropropanol to 2,3,3,3-tetrafluoro1-propene.

A 400 ml Hastelloy C shaker tube was charged with 26 g (0.4 mol) ofactivated Zinc powder, 33.3 g (0.2 mol) of2-chloro-2,3,3,3-tetrafluoropropanol, 30.6 g (0.3 mol) of aceticanhydride and 180 ml anhydrous DMF under N₂. Then the reaction mixturewas stirred at 50° C. for 6 hours. After the reaction mixture cooleddown to room temperature, the product was collected in a cold trapchilled by dry ice to produce 18.1 g of 2,3,3,3-tetrafluoropropene.

Example 3

Example 3 demonstrates the synthesis of 2,3,3,3-tetrafluoro-1-propenefrom 1,1,1,2-tetrafluoro-2,2-dichloroethane.

A 400 ml Hastelloy C shaker tube was charged with 20 g (0.315 mol) ofactivated Zinc powder, 7.5 g (0.25 mol) of paraformaldehyde and 130 mlanhydrous DMF under N₂. The tube was cooled down to −15° C. and 43 g(0.25 mol) of 1,1-dichlorotetrafluoroethane were added. Then thereaction mixture was stirred at 60° C. for 6 hours. After the reactionmixture cooled down to room temperature, 30 g (0.46 mol) of activatedZinc powder and 50 g (0.5 mol) of acetic anhydride were added into thereactor. The reaction mixture was stirred at 50° C. for 6 hr and thencooled down to room temp. The gas phase and the liquid phase wereanalyzed by GC-MS. Results are summarized in Table 2.

TABLE 2 GC area percent (%) Component (liquid phase)2,3,3,3-tetrafluoropropene 5.50 2-chloro-1,1,1,2-tetrafluoroethane 16.933,4,4,4-tetrafluoro-2-butanone 3.7 Acetyl fluoride 4.57 Methyl acetate4.72 Acetic acid 52.7 Acetic anhydride 4.88 Component (gas phase)2,3,3,3-tetrafluoropropene 83.42 Tetrafluoroethylene 0.751,1-difluoroethylene 0.28 Trifluoroethylene 1.692-chloro-1,1,1,2-tetrafluoroethane 11.62

Example 4

Example 4 demonstrates the synthesis of2-chloro-2,3,3,3-tetrafluoropropanol (CF₃CClFCH₂OH) in pyridine.

A 80 ml Fisher Porter tube was charged with 2.24 g (0.034 mol) ofactivated Zinc powder, 1.24 g (0.041 mol) of paraformaldehyde and 30 mlanhydrous pyridine under N₂. The tube was cooled down to −15° C. and 5 g(0.029 mol) of 1,1-dichlorotetrafluoroethane were added. Then thereaction mixture was stirred at 50° C. for 8 hours. The pressure of thereactor dropped to 8 psig at end of reaction from 25 psig. After thereaction mixture was cooled down to room temperature, it was analyzed byGC-MS. For GC-MS analysis, a portion of the reaction mixture wasacidified with a 10% solution of HCl in acetone. The data is reported byarea percent of GC-MS in table 3.

TABLE 3 Component GC-MS area percent (%)2-chloro-2,3,3,3-tetrafluoropropanol 8.5862-chloro-1,1,1,2-tetrafluoroethane 2.887 Methyl formate 0.420Chlorotrifluoroethylene 0.637 Trifluoroethylene .0140 Methanol 0.135Pyridine 87.194

Example 5

Example 5 demonstrates the synthesis of2-chloro-2,3,3,3-tetrafluoropropanol CF₃CClFCH₂OH in dimethylacetamide.

A 80 ml Fisher Porter tube was charged with 2.23 g (0.034 mol) ofactivated Zinc powder, 1.21 g (0.040 mol) of paraformaldehyde and 30 mlanhydrous dimethylacetamide under N₂. The tube was cooled down to −15°C. and 5.2 g (0.030 mol) of 1,1-dichlorotetrafluoroethane were added.Then the reaction mixture was stirred at 60° C. for 4.5 hours. Thepressure of the reactor dropped to 9 psig at end of reaction from 30psig. After the reaction mixture was cooled down to room temperature, itwas analyzed by GC-MS. For GC-MS analysis, a portion of the reactionmixture was acidified with a 10% solution of HCl in acetone. The data isreported by area percent of GC-MS in table 4.

TABLE 4 Component GC-MS area percent (%)2-chloro-2,3,3,3-tetrafluoropropanol 5.7502-chloro-1,1,1,2-tetrafluoroethane 2.181 Methyl formate 0.181Chlorotrifluoroethylene 2.634 Trifluoroethylene 0.029 Dimethylacetamide88.463

Example 6

Example 6 demonstrates the synthesis of2-chloro-2,3,3,3-tetrafluoropropanol CF₃CClFCH₂OH in pyridine, withpre-treatment of formaldehyde.

A 80 ml Fisher Porter tube was charged with 1.82 g (0.06 mol) ofparaformaldehyde and 30 ml anhydrous pyridine under N₂. The tube washeated up to 60° C. and stirred at 60° C. for 4 hr. Then it was cooleddown to room temp and 2.24 g (0.034 mol) of activated Zinc powder wereadded. After purging with N₂ for 15 min, the tube was cooled down to−15° C. and 5 g (0.029 mol) of 1,1-dichlorotetrafluoroethane were added.Then the reaction mixture was stirred at 50° C. for 8 hours. Thepressure of the reactor dropped to 9 psig at end of reaction from 25psig. After the reaction mixture was cooled down to room temperature, itwas analyzed by GC-MS. For GC-MS analysis, a portion of the reactionmixture was acidified with a 10% solution of HCl in acetone. The data isreported by area percent of GC-MS in Table 5. The selectivity of 114a toCF₃CClFCH₂OZnCl (analyzed as CF₃CClFCH₂OH) increased to 78.7%.

TABLE 5 (Liquid phase) Component GC-MS area percent (%)2,3,3,3-tetrafluoro-2-chloropropanol 12.062-chloro-1,1,1,2-tetrafluoroethane 3.07 Methyl formate 1.02 Methanol0.102 Trifluoroethylene 0.18 pyridine 83.55

Example 7

Example 7 illustrates the esterification of2,3,3,3-tetrafluoro-2-chloropropanol with acetic anhydride to produce2,3,3,3-tetrafluoro-2-chloropropyl acetate.

A 80 ml Fisher Porter tube was charged with 2 g (0.012 mol) ofCF₃CClFCH₂OH (which contains ˜15% diethyl ether), 1.35 g (0.0132) ofacetic anhydride and 0.25 g of concentrated sulfuric acid. The mixturewas stirred at 60° C. for 6 hr. After the reaction mixture was cooleddown to room temperature, it was analyzed by GC-MS. The data is reportedby area percent of GC-MS in Table 6. This result shows that more than99% of CF₃CClFCH₂OH has been converted to CF₃CClFCH₂OAc.

TABLE 6 Component GC-MS area percent (%)2,3,3,3-tetrafluoro-2-chloropropyl acetate 72.552,3,3,3-tetrafluoro-2-chloropropanol 0.198 Ethyl acetate 3.12 Aceticacid 17.24 Diethyl ether 6.19

Example 8

Example 8 illustrates the direct esterification of CF₃CClFCH₂OZnCl toCF₃CClFCH₂OAc.

10 ml of a pyridine solution containing about 14% CF₃CClFCH₂OZnCl wasvacuum evaporated at room temp to remove the majority of the pyridine.Then 2.0 g acetic anhydride and 1 ml DMF were added into the resultantsolid. The mixture was stirred at 60° C. for 7 hr. After the reactionmixture was cooled down to room temperature, it was analyzed by GC-MS.The data is reported by area percent of GC-MS in Table 7.

TABLE 7 Component GC-MS area percent (%)2,3,3,3-tetrafluoro-2-chloropropyl acetate 71.82,3,3,3-tetrafluoro-2-chloropropyl formate 2.012,3,3,3-tetrafluoro-2-chloropropanol 0.115 Acetic anhydride 2.61 Aceticacid 2.58 DMF/pyridine (solvent) 13.22

Example 9

Example 9 illustrates the conversion of CF₃CClFCH₂OAc to2,3,3,3-tetrafluoropropene.

The reaction mixture from example 8, above, was stirred with 1 g ofNa₂CO₃ to remove the acid generated in esterification step. Then 3 molof DMF and 1.3 g of Zn were added. The reaction was run in 80 ml FisherPorter tube at 50° C. for 2 hr and 60° C. for another 2 hr withstirring. The pressure of the reactor increased from 0 psig to 13 psig.After the reaction mixture was cooled down to room temperature, it wasanalyzed by GC-MS. The data is reported by area percent of GC-MS inTable 8. CF₃CClFCH₂OAc became non-detectable in the liquid phase of thereactor. This result shows that CF₃CClFCH₂OAc has been quantitativelyconverted to 2,3,3,3-tetrafluoropropene under the conditions above.

TABLE 8 GC-MS area percent (%) Component (vapor phase)2,3,3,3-tetrafluoropropene 94.48 2,3,3,3-tetrafluoro-2-chloropropanol0.115 Acetic anhydride 1.62 Methyl acetate 0.815 DMF 1.05 Pyridine 2.05(Liquid phase) 2,3,3,3-tetrafluoropropene 1.61 Acetic anhydride 1.45Methyl acetate 0.61 DMF 86.24 Pyridine 9.98

Example 10

Example 10 demonstrates the reaction of 1,1-dichlorotetrafluoroethanewith paraformaldehyde in a mixed solvent of dimethylforamide andpyridine to produce CF₃CClFCH₂OZnCl.

A 80 ml Fisher Porter tube was charged with 2.2 g Zn (0.037 mol), 0.3 gZinc acetate (0.0016 mol), 2 g (0.067 mol) of paraformaldehyde, 15 g ofanhydrous pyridine and 15 g of dimethylformamide under N₂. After N₂purge for 15 min, the tube was cooled down to −15° C. and 5 g (0.029mol) of 1,1-dichlorotetrafluoroethane were added. Then the reactionmixture was stirred at 50° C. for 2 hours. The pressure of the reactordropped to 5 psig at end of reaction from 25 psig. After the reactionmixture cooled down to room temperature, it was analyzed by GC-MS. ForGC-MS analysis, a portion of the reaction mixture was acidified with a10% solution of HCl in acetone. Solvents DMF and pyridine are excludedfrom integration. The data is reported by area percent of GC-MS. Theselectivity of 114a to CF₃CClFCH₂OZnCl (analyzed as CF₃CClFCH₂OH) is 83%based on GC-MS analysis.

TABLE 9 (Liquid phase) 2-chloro-1,1,1,2- 2,3,3,3- 2,3,3,3- 2,3,3,3-Acetic Methyl Methyl tetrafluoro tetrafluoro- tetrafluoro-2-tetrafluoro-2- Trifluoroethylene acid formate acetate ethane propenechloropropanol chloropropyl acetate 0.18% 3.1% 0.24% 0.68% 5.18% 4.61%80.1% 3.744%

Example 11

Example 11 illustrates esterification of CF₃CClFCH₂OZnCl directly toCF₃CClFCH₂OAc with acetic anhydride in a solvent mixture.

Excess Zn was filtrated off from the reaction mixture from example 10,then was charged into a 80 ml Fisher Porter tube. 4.4 g of aceticanhydride (0.043 mol) were also added into the reactor. The mixture wasstirred at 60° C. for 6 hr. After the reaction mixture cooled down toroom temperature, it was analyzed by GC-MS. The data is reported by areapercent of GC-MS in Table 10. Solvents DMF, pyridine and aceticanhydride are excluded from integration. This result shows that morethan 94% of CF₃CClFCH₂OZnCl has been converted to CF₃CClFCH₂OAc atcondition above.

TABLE 10 Liquid phase 2-chloro-1,1,1,2- 3-chloro-3,4,4,4- Ethyl2-chloro-2,3,3,3- tetrafluoro trifluoro- methyl Methyl tetrafluoropropylTrifluoroethylene ethane 2-butanone ether acetate acetate unknows 0.477%5.97% 2.57% 0.83% 0.92% 85.3% 2.46%

Example 12

Example 12 illustrates the synthesis of 2,3,3,3-tetrafluoro1-propenefrom 1,1,1,2-tetrafluoro-2,2-dichloroethane in 3:1 pyridine:DMF solvent.

A 80 ml Fisher Porter tube was charged with 2.1 g Zn (0.032), 0.3 g Zincacetate (0.0016 mol), 2 g (0.067 mol) of paraformaldehyde, 30 ganhydrous pyridine under N₂. After purging with N₂ for 15 min, the tubewas cooled down to −15° C. and 5 g (0.029 mol) of1,1-dichlorotetrafluoroethane were added. Then the reaction mixture wasstirred at 50° C. for 3 hours. The pressure of the reactor dropped to5.5 psig at end of reaction from 25 psig. After the reaction mixturecooled down to room temperature, it was analyzed by GC-MS. For GC-MSanalysis, a portion of the reaction mixture was acidified with a 10%solution of HCl in acetone. Solvent pyridine was excluded fromintegration. The data is reported in Table 11 by area percent of GC-MS.The selectivity of 1,1-dichlorotetrafluoroethane to CF₃CClFCH₂OZnCl(analyzed as CF₃CClFCH₂OH) is 81% based on GC-MS analysis.

Then the excess Zn was filtrated off from the reaction mix and it wascharged into a 80 ml Fisher Porter tube. 10 ml Anhydrous DMF and 3.5 gof acetic anhydride (0.034 mol) were also added into the reactor. Themixture was stirred at 60° C. for 4 hrs. After the reaction mixturecooled down to room temperature, it was analyzed by GC-MS. The data isreported in Table 12 by area percent of GC-MS. Solvents DMF and pyridineare excluded from integration. This result shows that more than 98% ofCF₃CClFCH₂OZnCl has been converted, and selectivity to CF₃CClFCH₂OAc andCF₃CFClCH₂OCH₂OAc are 89%.

10 ml of reaction mix above was left in an 80 ml Fisher Porter tube,activated Zinc powder (1 g, 0.015 mol) was also added. The reaction wasrun in 80 ml Fisher Porter tube at 60° C. for 4 hr with stirring. Thepressure of the reactor increased from 6 psig to 15.5 psig. After thereaction mixture cooled down to room temperature, it was analyzed byGC-MS. The data is reported by area percent of GC-MS. The result ofvapor phase was listed in Table 13 and the result of liquid phase wasreported in Table 14 (solvent DMF and pyridine was excluded fromintegration). CF₃CClFCH₂OAc became non-detectable in liquid phase ofreactor. Analysis shows that selectivity to2,3,3,3-tetrafluoro-1-propene is about 94%, and selectivity to1,3-bis-trifluoromethyl-1,3-difluorocyclobutane (C₆H₄F₈) is about 5%.

TABLE 11 Compounds GC-MS area % Trifluoroethylene 1.93Trifluoroacetaldehyde 1.05 2-Chloro-1,1,1,2-tetrafluoro ethane 12.771,1-Dichloro-1,2,2,2-tetrafluoroethane 0.3782,3,3,3-tetrafluoro-2-chloropropanol 74.682,3,3,3-tetrafluoro-2-chloropropyl acetate 1.648 Unknowns 6.39

TABLE 12 Compounds GC-MS area % Trifluoroethylene 0.682,3,3,3-tetrafluoropropene 0.04 2-Chloro-1,1,1,2-tetrafluoro ethane 8.741,1-Dichloro-1,2,2,2-tetrafluoroethane 1.033-chloro-3,4,4,4-tetrafluoro-2-butanone 1.445 2,3,3,3-tetrafluoropropylacetate 0.31 2,3,3,3-tetrafluoro-2-chloropropanol 1.672,3,3,3-tetrafluoro-2-chloropropyl acetate 65.39 Acetic anhydride 3.332-chloro-2,3,3,3-tetrafluoropropoxy methyl 6.47 acetate Unknowns 7.42

TABLE 13 Compounds GC-MS area % Tetrafluoroethylene 0.08Trifluoroethylene 5.84 1,1,1-trifluoroethane 0.022,3,3,3-tetrafluoropropene 79.93 Chlorotrifluoroethylene 0.062-Chloro-1,1,1,2-tetrafluoro ethane 9.10 C₆H₄F₈ 4.002,3,3,3-tetrafluoropropyl acetate 0.1 Unknowns 0.85

Example 13

Example 13 illustrates the synthesis of 2,3,3,3-tetrafluoro-1-propenefrom 1,1,1,2-tetrafluoro-2,2-dichloroethane in 1:1 pyridine:DMF solvent.

A 80 ml Fisher Porter tube was charged with 2.1 g Zn (0.032), 0.3 g Zincacetate (0.0016 mol), 2 g (0.067 mol) of paraformaldehyde, 0.2 gBis(hydrogenated alkyl)dimethyl ammonium acetate and 30 g anhydrouspyridine under N₂. After purging with N₂ for 15 min, the tube was cooleddown to −15° C. and 5 g (0.029 mol) of 1,1-dichlorotetrafluoroethanewere added. Then the reaction mixture was stirred at 50° C. for 3 hours.The pressure of the reactor dropped to 5.5 psig at end of reaction from23 psig. After the reaction mixture cooled down to room temperature, itwas analyzed by GC-MS. For GC-MS analysis, a portion of the reactionmixture was acidified with a 10% solution of HCl in acetone. SolventsDMF and pyridine are excluded from integration. The data is reported inTable 15 by area percent of GC-MS. The selectivity of 114a toCF₃CClFCH₂OZnCl (analyzed as CF₃CClFCH₂OH) is about 85% based on GC-MSanalysis.

Then 10 ml reaction mix was filtrated and charged into an 80 ml FisherPorter tube. 10 ml anhydrous DMF and 3.5 g of acetic anhydride (0.034mol) were also added into the reactor. The mixture was stirred at 60° C.for 4 hrs. After the reaction mixture cooled down to room temperature,it was analyzed by GC-MS. The data is reported in Table 16 by areapercent of GC-MS. Solvents DMF and pyridine are excluded fromintegration. This result shows that more than 98% of CF₃CClFCH₂OZnCl hasbeen converted, and selectivity to CF₃CClFCH₂OAc and CF₃CFClCH₂OCH₂OAcare about 95%.

The reaction mix above was treated with 2 g Na₂CO₃ in 80 ml FisherPorter tube. After Na₂CO₃ was filtrated off, activated Zinc powder (1 g,0.015 mol) was added. The reaction was run in an 80 ml Fisher Portertube at 60° C. for 4 hr with stirring. The pressure of the reactorincreased from 5 psig to 18 psig. After the reaction mixture cooled downto room temperature, it was analyzed by GC-MS. The data is reported byarea percent of GC-MS. The result of vapor phase was listed in Table 17and the result of liquid phase was reported in Table 18 (solvent DMF andpyridine was excluded from integration). More than 99% CF₃CClFCH₂OAc andmore than 95% CF₃CFClCH₂OCH₂OAc have been converted. Analysis shows thatselectivity to 1234yf is about 98%, and selectivity to1,3-bis-trifluoromethyl-1,3-difluorocyclobutane (C₆H₄F₈) is about 0.1%.

TABLE 14 Compounds GC-MS area % Trifluoroethylene 1.06Trifluoroacetaldehyde 0.09 2,3,3,3-tetrafluoropropene 0.032-Chloro-1,1,1,2-tetrafluoro ethane 8.331,1-Dichloro-1,2,2,2-tetrafluoroethane 1.552,3,3,3-tetrafluoro-2-chloropropanol 85.702,3,3,3-tetrafluoro-2-chloropropyl acetate 0.285 Unknowns 0.656

TABLE 15 Compounds GC-MS area % 2-Chloro-1,1,1,2-tetrafluoro ethane 3.171,1-Dichloro-1,2,2,2-tetrafluoroethane 0.623-chloro-3,4,4,4-tetrafluoro-2-butanone 0.322,3,3,3-tetrafluoro-2-chloropropanol 1.742,3,3,3-tetrafluoro-2-chloropropyl acetate 68.002-chloro-2,3,3,3-tetrafluoropropoxy methyl 7.63 acetate Unknowns 1.32

TABLE 16 Compounds GC-MS area % Trifluoroethylene 0.722,3,3,3-tetrafluoropropene 97.46 Chlorotrifluoroethylene 0.06 C₆H₄F₈ 0.1Unknowns 0.1

TABLE 17 Compounds GC-MS area % Trifluoroethane 0.032,3,3,3-tetrafluoropropene 35.26 2-Chloro-1,1,1,2-tetrafluoro ethane5.89 C₆H₄F₈ 0.25 2,3,3,3-tetrafluoro-2-chloropropanol 0.222,3,3-trifluoro-2-propen-1-ol acetate 1.042,3,3,3-tetrafluoro-2-chloropropyl acetate 0.7 2,3,3,3-tetrafluoropropylacetate 0.42 2-chloro-2,3,3,3-tetrafluoropropoxy methyl 2.27 acetateUnknowns 7.49

Example 14

Example 14 illustrates the synthesis of 2,3,3,4,4,4-hexafluoro-1-butenefrom 1,1,1,2,2,3-hexafluoro-3,3-dichloropropane in 1:1 pyridine:DMFsolvent.

A 80 ml Fisher Porter tube is charged with 2.1 g Zn (0.032), 0.3 g Zincacetate (0.0016 mol), 2 g (0.067 mol) of paraformaldehyde, 0.2 gBis(hydrogenated alkyl)dimethyl ammonium acetate and 30 g anhydrouspyridine under N₂. After purging with N₂ for 15 min, the tube is cooleddown to −15° C. and 6.4 g (0.029 mol) of1,1,1,2,2,3-hexafluoro-3,3-dichloropropane was added. Then the reactionmixture is stirred at 50° C. for 3 hours. The pressure of the reactordrops to 5.5 psig at end of reaction from 23 psig. After the reactionmixture cooled down to room temperature, it is analyzed by GC-MS. ForGC-MS analysis, a portion of the reaction mixture is acidified with a10% solution of HCl in acetone. Solvents DMF and pyridine are excludedfrom integration. The data is reported in Table 18 by area percent ofGC-MS. The selectivity of 216cb to CF₃CF₂CClFCH₂OZnCl (analyzed asCF₃CF₂CClFCH₂OH) is about 85% based on GC-MS analysis.

Then 10 ml reaction mix is filtrated and charged into an 80 ml FisherPorter tube. 10 ml anhydrous DMF and 3.5 g of acetic anhydride (0.034mol) are also added into the reactor. The mixture is stirred at 60° C.for 4 hrs. After the reaction mixture cooled down to room temperature,it is analyzed by GC-MS. The data is reported in Table 19 by areapercent of GC-MS. Solvents DMF and pyridine are excluded fromintegration. This result shows that more than 98% of CF₃CF₂CClFCH₂OZnClis converted and selectivity to CF₃CF₂CClFCH₂OAc andCF₃CF₂CFClCH₂OCH₂OAc are about 95%.

The reaction mix above is then treated with 2 g Na₂CO₃ in an 80 mlFisher Porter tube. After Na₂CO₃ is filtrated off, activated Zinc powder(1 g, 0.015 mol) is added. The reaction is run in an 80 ml Fisher Portertube at 60° C. for 4 hr with stirring. The pressure of the reactorincreases from 5 psig to 18 psig. After the reaction mixture is cooleddown to room temperature, it is analyzed by GC-MS. The data is reportedby area percent of GC-MS. The result of vapor phase is listed in Table20 and the result of liquid phase is reported in Table 21 (solvent DMFand pyridine was excluded from integration). More than 99%CF₃CF₂CClFCH₂OAc and more than 95% CF₃CF₂CFClCH₂OCH₂OAc are converted.Analysis shows that selectivity to 2,3,3,4,4,4-hexafluoro-1-butene isabout 98%, and selectivity to1,3-bis-pentafluoroethyl-1,3-difluorocyclobutane (C₈H₄F₁₂) is about0.1%.

TABLE 18 Compounds GC-MS area % 1,2,3,3,3-pentafluoro-1-propene 0.91,1,1,2,2,3-hexafluoro-3-chloropropane 7.11,1,1,2,2,3-hexafluoro-3,3-dichloropropane 1.5 CF₃CF₂CFClCH₂OH 84CF₃CF₂CFClCH₂OAc 0.3 Unknowns 0.9

TABLE 19 Compounds GC-MS area % 1,1,1,2,2,3-hexafluoro-3-chloropropane2.5 CF₃CF₂CFClCH₂OH 1.2 CF₃CF₂CFClCH₂OAc 732-chloro-2,3,3,4,4,4-hexafluorobutoxy methyl 5.2 acetate Unknowns 17

TABLE 20 Compounds GC-MS area % 1,2,3,3,3-pentafluoro-1-propene 0.52,3,3,4,4,4-hexafluoro-1-butene 96.5 C₈H₄F₁₂ 0.1 Unknowns 0.1

TABLE 21 Compounds GC-MS area % 2,3,3,4,4,4-hexafluoro-1-butene 35.263-chloro-1,1,1,2,2,3-hexafluoropropane 6.3 C₈H₄F₁₂ 0.62,3,3,4,4,4-hexafluoro-2-chloropropanol 0.82,3,4,4,4-pentafluoro-2-propen-1-ol acetate 1.4 CF₃CF₂CFClCH₂OAc 0.62-chloro-2,3,3,4,4,4-hexafluoropropoxy methyl 1.8 acetate Unknowns 7.8

Note that not all of the activities described above in the generaldescription or the examples are required, that a portion of a specificactivity may not be required, and that one or more further activitiesmay be performed in addition to those described. Still further, theorder in which activities are listed are not necessarily the order inwhich they are performed.

In the foregoing specification, the concepts have been described withreference to specific embodiments. However, one of ordinary skill in theart appreciates that various modifications and changes can be madewithout departing from the scope of the invention as set forth in theclaims below. Accordingly, the specification and figures are to beregarded in an illustrative rather than a restrictive sense, and allsuch modifications are intended to be included within the scope ofinvention.

Benefits, other advantages, and solutions to problems have beendescribed above with regard to specific embodiments. However, thebenefits, advantages, solutions to problems, and any feature(s) that maycause any benefit, advantage, or solution to occur or become morepronounced are not to be construed as a critical, required, or essentialfeature of any or all the claims.

It is to be appreciated that certain features are, for clarity,described herein in the context of separate embodiments, may also beprovided in combination in a single embodiment. Conversely, variousfeatures that are, for brevity, described in the context of a singleembodiment, may also be provided separately or in any subcombination.Further, reference to values stated in ranges include each and everyvalue within that range.

1. A process for the manufacture of hydrofluoroalkenes of the structureR_(f)CF═CHR, comprising reacting a hydrofluoroalkanol of structureR_(f)CFXCHROH or a hydrofluoroalkoxide of structure R_(f)CFXCHROMX,wherein M is a reactive metal in the +2 oxidation state, with acarboxylic acid anhydride and a reactive metal in a reaction solvent toform a hydrofluoroalkene, wherein R_(f) is selected from the groupconsisting of perfluoromethyl, perfluoroethyl, perfluoro-n-propyl,perfluoro-i-propyl, perfluoeo-n-butyl and perfluoro-i-butyl, X isselected Cl, Br and I, and R is selected from the group consisting of H,CH₃, C₂H₅, n-C₃H₇, and i-C₃H₇.
 2. The process of claim 1, furthercomprising the step of isolating said hydrofluoroalkene.
 3. The processof claim 2 wherein R_(f) is CF₃ and R is H.
 4. The process of claim 1wherein the carboxylic acid anhydride is selected from the groupconsisting of acetic anhydride, propionic anhydride, butyric anhydride,succinic anhydride, glutaric anhydride, adipic anhydride and formicanhydride.
 5. The process of claim 1 wherein the reactive metal isselected from the group consisting of magnesium turnings, activated zincpowder, aluminum, and a powder of any of the following metals:magnesium, calcium, titanium, iron, cobalt, nickel, copper, zinc indium,and combinations thereof.